Process for preparing an alternating copolymer of an alpha-olefin and butadiene

ABSTRACT

ALTERNATING COPOLYMERS OF AN A-OLEFIN BUTADIENE ARE FORMED BY REACTION IN THE PRESENCE OF A CATALYST COMPRISING AN ORGANOALUMINUM COMPOUND HAVING THE FORMULA ALR3 WHEREIN R REPRESENTS A C1-C12 HYDROCARBON RADICAL SELECTED FROM THE GROUP CONSISTING OF ALKYL, CYCLOALKYL, ARYL AND ARALKYL RADICALS AND AN ORGANOTITANIUM COMPOUND HAVING   TI-X-OOC-R   STRUCTURE IN THE MOLECULE WHEREIN R IS AS DEFINED ABOVE AND X IS HALOGEN.

United States Patent 3,737,416 PROCESS FOR PREPARING AN ALTERNATING COPOLYMER OF AN a-OLEFIN AND BUTADIENE Kiyoshige Hayashi, Tokyo, and Akihiro Kawasaki and Isao Maruyama, Ichihara-shi, Japan, assignors to Maruzen Petrochemical Co., Ltd., Tokyo, Japan N0 Drawing. Filed Mar. 3, 1971, Ser. No. 120,405 Claims priority, application Japan, Mar. 17, 1970, 45/21,994, 45/21,995; July 24, 1970, 45/64,?144, 45/64,345; Nov. 6, 1970, 45/97,132, 45/97,133

Int. Cl. C08d 1/14, 3/06, 3/02 U.S. Cl. 26082.1 13 Claims ABSTRACT OF THE DISCLOSURE Alternating copolymers of an u-olefin butadiene are formed by reaction in the presence of a catalyst comprising an organoaluminum compound having the formula AlR wherein R represents a C C hydrocarbon radical selected from the group consisting of alkyl, cycloalkyl, aryl and aralkyl radicals and an organotitanium compound having 0 TiXoiiR structure in the molecule wherein R is as defined above and X is halogen.

RELATED APPLICATION This application is related to application Ser. No. 140,552, filed May 5, 1971, wherein alternating copolymers of C -C conjugated dienes and a-olefins, and a process for preparing the same, are described.

BACKGROUND OF THE INVENTION (1) Field of the invention The present invention relates to a process for preparing an alternating copolymer of an a-olefin having the general formula of CH CHR wherein R represents a C C hydrocarbon radical selected from the group consisting of alkyl, cycloalkyl, aryl and aralkyl radicals and butadiene and a novel alternating copolymer of butadiene and said a-olefin.

(2) Description of the prior art In order to obtain new and useful synthetic elastomers, many attempts have been made to produce alternating copolymer of a conjugated diene and an a-olefin. However, the copolymerization reaction is very difiicult and, in general, it is not easy to produce even a random copolymer of conjugated diene and a-olefin by an ionic catalyst.

For example, Belgian Pat. 546,150 reports a process for preparing an amorphous copolymer of butadiene and an a-olefin having more than 3 carbon atoms by using a catalyst systems of trialkylaluminum and titanium tetrachloride at 50 C. The copolymer was determined to be amorphous from their X-ray measurements. The chemical configuration of the copolymer is not stereospecific. On the other hand, for example, an alternating copolymer of butadiene and propylene is also shown to be amorphous from its X-ray spectrum at room temperature, but it is a stereospecific copolymer and therefore it can crystallize on stretching or on cooling.

British Pat. 1,026,615 claims a process for preparing a random copolymer of butadiene and propylene by forming a catalyst system of trialkylaluminum and titanium tetrachloride in the presence of propylene, and then adding butadiene to the catalyst system. According to the patent, the propylene content of the copolymer was much higher than that of the copolymer prepared by the catalyst system formed in the absence of propylene. The patent 3,737,416 Patented June 5, 1973 "ice Q also describes that analysis has shown that the copolymer obtained is a random copolymer and not blocked copolymer, but there are shown no experimental results which support the assumption.

British Pat. 1,108,630 shows a process for preparing a rubbery random copolymer of butadiene and propylene of high molecular weight with high content of propylene by using a three components catalyst system consisting of trialkylaluminum, iodine and a compound having the general formula of TiBr Cl wherein n is zero or an integer of 1 to 4. The microstructure of butadiene unit and the content of propylene unit in the copolymer are shown in the patent. But there are shown no experimental results which support the assumption that the copolymer should be a random copolymer of butadiene and propylene. A random copolymer of butadiene and propylene was also prepared by using a catalyst system consisting of triethylaluminum, titanium tetrachloride and polypropylene oxide. Polypropylene oxide was used as a randomizer and a copolymer of butadiene and propylene prepared by the catalyst system of triethylaluminum and titanium tetrachloride was shown to be block type from the results of oxidative decomposition reaction of the copolymer (Paper presented at 2nd Symposium on Polymer Synthesis, Tokyo, Oct. 5, 1968, The Society of Polymer Science, Japan).

At any rate, all of the methods described above relate to the methods for preparing a nonstereospecific or atactic copolymer. On the other hand, an alternating copolymer is stereospecific one and therefore these methods are not pertinent to the process of this invention.

Recently, Furukawa et. al. reported a process for preparing an alternating copolymer of butadiene and an aolefin by using vanadyl (V) chloride-diethylaluminum monochloride-triethylaluminum catalyst system (22nd Annual Meeting of Japan Chemical Society, Tokyo, Mar. 31, 1969; I. Polymer Sci., B7, 671 (1969).

The methods for preparing an alternating copolymer of butadiene and an ot-olefin by using an organoaluminum compound-vanadium (IV) chloride or vanadium (V) oxychloride-organic peroxide or chromium (VI) oxychloride catalyst system (Ger. Otfen. 1,963,780), an organoaluminum compound-a vanadium compound having no vanadium-halogen linkage-a halogen compound catalyst system (Ger. Olfen. 1,964,706; I. Polymer Science, B7, 613 (1969)) and an organoaluminum compound-a vanadium-halogen linkage-a compound having MOR (M is an atom whose electronegativity is less than 2.2 and R is a hydrogen radical) linkage catalyst system (Ger. Oifen. 2,020,168; Neth, appl. 7006067) were all proposed by us previously.

In short, the catalyst systems for alternating copolymerization described above employ an organoaluminum compound and a vanadium compound as indispensable elements of the catalyst systems. The microstructure of butadiene units in the alternating copolymer of butadiene and an u-olefin prepared by these catalyst systems was almost all trans-1,4-configuration, occasionally involving minor amounts of 1,2-configuration.

On the other hand, the most recently, we proposed the process for preparing an alternating copolymer of butadiene and an a-olefin by using the three components catalyst system of an organoaluminum compound, titanium tetrahalide and a carbonyl group containing compound Ger. Otfen. 2,023,405, Neth, appl. 7006877). The alternating copolymer prepared by this catalyst system contains considerable amounts of cis-1,4-configuration butadiene unit, occasionally involving minor amounts of cis- 1,2-configuration and moreover molecular weight of the alternating copolymer is remarkably higher than that of the one prepared by the organoaluminum-vanadium compound type catalyst system described above.

As far as the inventors know, with the exception of the methods described above, there is found to be no prior art in connection with an alternating copolymer of a conjugated diene and an a-olefin nor of a process for the preparation thereof.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a process for preparing an alternating copolymer of butadiene and an a-olefin having a high molecular weight in a good yield.

It is a further object of this invention to provide a catalyst system giving high molecular weight alternating copolymer of butadiene and an a-olefin in a good yield.

In accordance with this invention, we have found that a high molecular weight alternating copolymer of butadiene and an a-olefin can be produced in a good yield by using a catalyst system comprising of the first component of an organoaluminum compound having the general formula of AlR wherein R represents a hydrocarbon radical selected from the group consisting of a C -C preferably C -C and more preferably C -C alkyl, cycloalkyl, aryl and aralkyl radicals and the second component of an organotitanium compound having ll TIXOCR (R is the same one as described above and X is a halogen) structure in the molecule or the catalyst system composed of the first component of an organoaluminum compound having the general formula of Al-R wherein R is as defined above, the second component of an organotitanium compound having (R and X are as described above) structure in the molecule and the third component of halogen, a halogen compound or a mixture thereof.

The alternating copolymers of this invention are rubber-like in character and can be used as polymeric plasticizers, in adhesives and can be vulcanized with sulfur or a sulfur compound to produce vulcanized elastomers.

The organoaluminum compounds which form the first component of the catalyst system of this invention are defined by the formula AlR wherein R is a hydrocarbon radical selected from the group consisting of a C C preferably C -C and more preferably C -C alkyl, cycloalkyl, aryl and aralkyl radicals. Mixtures of these organoaluminum compounds may also be employed. Specific examples of compounds represented by the formula include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri 11 butylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri p tolylaluminum, tribenzylaluminum, ethyldiphenylaluminum, ethyl di-p-tolylaluminum, ethyl dibenzylaluminum, diethylphenylaluminum, diethylp-tolylaluminum, diethyl benzylaluminum and the like. Mixtures of these compounds may also be employed. Of these, it is usually preferred to employ trialkylaluminum compounds.

The organotitanium compounds having it TiXOOR (R is a hydrocarbon radical selected from the group consisting of a C -C preferably C -C and more preferably C -C alkyl, cycloalkyl, aryl and aralkyl radicals and X is halogen) structure in the molecule and forming the second component of the catalyst system of this invention, by no means limiting, are compounds shown by the general formulae of i i i TiX(OCR a, TiXg(OCR z, TiXa OCR 0 TiX(OR)z(O ER) etc. and mixtures thereof.

A mixture of an organotitanium compound having TiOR (R is as defined above) structure and having no TiX linkage in the molecule and halogen, a halogen compound or a mixture thereof can be used as the second component of the catalyst of this invention, provided that said organotitanium compound can react with halogen, said halogen compound or the mixture thereof to produce an organotitanium compound having 0 TlXOPJR structure, in situ. Examples of such 0 'rioim structure containing compounds, by no means limiting, are the compounds shown by the general formulae of structure to the second component of the catalyst system, by no means limiting, are the ones showing Lewis acid property such as compounds of the general formulae VX (X is halogen hereinafter the same), VOX WX MoX CIO X ZI'X4, FCXg, BX3, PX5, SDX4, SbX5, .A1X3, CuX, MnX MgX ZnX HgX BiX- NiX etc.; Lewis base complex compounds of the above mentioned halogen compounds showing Lewis acid property such as compounds of the general formulae AlX -O'(C H VOX -O(C H FeX -O(C H NiX -Py (Py represents pyridine), HgX -Py, etc.; organoaluminum compounds having A1-X linkage such as compounds of (n is a number from 1 to 2 and R is as defined above), AIR,,X (n is a number from 1 to 2 and R is as defined above), etc.; organotransition metal compounds having transition metalX linkage such as compounds of the general formulae OV(OR),,X (n is a number from 1 to 2), Ti(OR) X n is a number from l to :5),

Zr(OR) X, OV(C5H7O2) X3 (n is a number from 1 to 2), V(C H ),,X (n is a number from 1 to 2),

(C H IrX etc.; acid halide; compounds having the general formula of halogenated alkane compounds such as tert-butyl halide, sec-butyl halide, carbon tetrahalide, etc. and a mixture thereof.

The components of the catalyst system are normally employed in catalytic quantities. In the preferred embodiment the molar ratio of organoaluminum compound which forms the first component of the catalyst system of the present invention to organotitanium compound which forms'the second component of the catalyst system should be in the range of 200 to 1 (200 Al/Ti 1), the optimum ratios will be found between 100 and 2 (l00 Al/Ti 2).

In the preferred embodiment, the atomic ratio of titanium atom in the catalyst system of the present invention to halogen atom in the catalyst system should be in the range of 0.01 to 20 (0.01 Ti/X 20), the optimum ratios will be found between 0.02 and The a-olefin used in this invention is one having the general formula:

CH =CHR of the catalyst system may be mixed at a temperature within a very wide range from 100 C. to -+100 C.,

' and preferably from 78 C. to +50 C. This temperawherein R is a hydrocarbon radical selected from the group consisting of a C -C preferably C -C and more preferably C -C alkyl, cycloalkyl, aryl and aralkyl radical. Specific examples of compounds represented by the formula include propylene, butene 1, pentene l, 4-methyl-pentene-1, hexene-l, 4-methyl-hexene-l, S-methyl-hexene-l, heptene-l, 5 methylheptene- 1, octene-l, decene-l, vinylcyclohexane, 4-methyl-l-vinylcyclohexane, styrene and the like. Mixtures of these a-olefin monomers may also be employed.

The molar ratio of conjugated diene to a-olefin in the initial monomer composition is not critical, but is usually within the range of 10/1 to 1/ 100 (10/1 diene/a-olefin 1/100), preferably be 10/2 to 1/50 (l0/2 diene/a- 0lefin 1/50). It is noteworthy that, for example, when copolymerization reaction proceeds 50% by using a monomer mixture having the initial monomer composition of 1:50, the molar ratio of unreacted butadiene to unreacted a-olefin at this stage should be 1:99.

The manner for preparing the catalyst system of this invention has not been found to be critical. The organoaluminum compound which forms the first component of the catalyst system and the organotitanium compound which forms the second component of the catalyst system or the organoaluminum compound, the organotitanium compound and the halogen 'or halogen compound which forms the third component of the catalyst system of the present invention can be mixed per se or they can be mixed in the presence of an organic solvent. If a solvent is to be employed, the aromatic solvent such as benzene, toluene, xylene, etc.; the aliphatic hydrocarbon, e.g. propane, butane, pentane, hexane, heptane, cyclohexane, etc.; the halogenated hydrocarbon solventv such as trihaloethane, methylene halide, tetrahaloethylene, etc. are usually peferred.

In general, the organoaluminum compound which forms the first component of the catalyst system and the organotitanium compound which forms the second component 'ture is shown as catalyst preparation temperature in the tables given hereinafter. The halogen or halogen compound which forms the third component of the catalyst system may be mixed with the other one or two compo nents of the catalyst system of this invention at a temperature within a very wide range from C. to +100 C., and preferably from 78 C. to +50 C.

The polymerization reaction may be carried out at a temperature within a range from 100 C. to +100 C., and preferably from 78 C. to +50 C.

The practice of this copolymerization is usually carried out in the presence of an organic solvent or diluent. However, this does not mean that this invention cannot be practiced in the form of bulk polymerization, i.e. without the use of solvent. If it is desired to use a solvent, the aromatic solvent such as benzene, toluene, xylene, etc.; the aliphatic hydrocarbon, e.g. propane, butane, pentane, hexane, heptane, cyclohexane, etc.; halogenated hydrocarbon solvent such as trihaloethane, methylene halide, tetrahaloethylene and the like may also be employed.

At the completion of the copolymerization reaction, the prduct may be precipitated and deashed by using a methanol-hydrochloric acid mixture. The precipitated product may be further washed with methanol for several times and dried under vacuum.

The catalyst system of the present invention employs an organoaluminum compound and a titanium compound as main components and in different from the alternating copolymer of butadiene and an a-olefin prepared by the organoaluminum-vanadium compound type catalyst system, the butadiene units of the alternating copolymer of butadiene and the wolefin prepared by the methods of this invention contains considerable amounts of cis-1,4- structure and occasionally involves minor amounts of 1,2- structure. In other words, the structure of the alternating copolymer of butadiene and a-olefin prepared by the method of this invention resembles to that of the one prepared by the catalyst system of an organoaluminum compound, titanium tetrahalide and a carbonyl group containing compound (Ger. Oflen. 2,023,405, Neth. appl. 7006877).

The invention will be illustrated with reference to the following examples.

EXAMPLE 1 The usual, dry, air-free technique was employed and 0.16 millimole organotitanium compound, 6.5 milliliters toluene and 0.2 millimole halogen compound were put successively into 25 milliliter glass bottles at 25 C. Then, the bottles were left alone at 25 C. for 10 minutes. Thereafter, the bottles were held in a low temperature bath at 78 C. (it corresponds to catalyst preparation temperature shown in Table 1) and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2.0 milliliters liquid propylene, 2 milliliters liquid butadiene and 2.0 milliliters toluene were put successively into the bottles also employing the usual, dry, air-free technique. Thereafter, the bottles were sealed and allowed to copolymerize at 30 C. for 16 hours. The results were summarized in Table l.

The molecular weight of the MEK soluble fraction of the alternating copolymer was lower than that of the MEK insoluble and diethyl ether soluble fraction of the alternating copolymer. Therefore, it is concluded that the yield of the high molecular Weight fraction in Exp. No. 4 obtained by the two components catalyst system of II AmBma-riouo CCHs is lower than that of the ones in Exp. No. 1-3 obtained by the three components catalyst systems of 0 II A1(iB u) ;-TiC1 O C CHa-halogcn compound.

TABLE 1 Oatalysts* Yield of alternating Organotitanium copolymer of butacompound diene and propylene Catalyst Polymerization preparaconditions MEK insoltion MEK uble, diethyl TiOlBO CH3 Halogen or tempera- Temperasoluble other soluble Aid-Bu); halogen ture ture Time fraction fractio Example number (mmol) (mmol) compound Mmol 0.) 0.) (hr.) (g.)

2. 0 0. 16 SnClr 0.2 78 -30 16 0.16 1. 09 2.0 0.16 BFa-OEtz 0.2 78 80 16 0.40 0.61 2. 0 0.16 CoHsCOCl 0. 2 78 30 16 0. 24 0. 58 2. 0 0. l6 78 30 16 0. 40 0. 34

*Al(i-Bu)a=triisobutylaluminum, BF -OET2=b0r0n trifluoride etherate, (3611500 Cl=benzoyl chloride.

EXAMPLE 2 8.0 milliliters toluene and varying amounts of organoti- The usual, dry, air-free technique was employed and tamum compound 0.2 millimole organotitanium compound, 6.5 milliliters toluene and 0.5 millimole halogen or halogen compound H were put successively into 25 milliliter glass bottles at 20 (1101300011115) 25 C. Then the bottles were left alone at 25 C. for minutes. Thereafter, the bottles were held in a low temperature bath at 78 C. (it corresponds to catalyst preparation temperature shown in Table 2) and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2.0 milliliters liquid propylene, 2.0 milliliters liquid butadiene and 2.0 milliliters toluene were put successively into the bottles also employing the usual, dry, air-free technique. Thereafter, the bottles were sealed and allowed to copolymerize at 30 C. for 16 hours. The results were summarized in Table 2.

were put successively into 25 milliliter glass bottles at C. Then, the bottles were held in a constant temperature bath showing a predetermined temperature (it corresponds to catalyst preparation temperature given in Table 3 listed below) and varying amounts of organealuminum compound solution in toluene (1 molar solu tion) were put into the bottles. Thereafter, the bottles were held in a low temperature bath at 78 C. and a mixture of 2.0 milliliters liquid propylene, 2.0 milliliters liquid butadiene and 2 milliliters toluene was put into the g g gg g ggg figi i Shown m Refs 1 and 2 gave no bottles also employing the usual, dry, air-free technique. EXAMPLE 3 Then, the bottles were sealed and allowed to copolymerize at predetermined temperature and for predeter- The usual, dry, air-free technique was employed and mined time. The results were summarized in Table 3.

TABLE 2 Yield of alternating copolymer of butadiene Catalyst Polymerization and propylene Catalysts preparaconditions tion MEK MEK insol- Halogen or tcmpera- Temperasoluble uble, d ethyl AKi-Bu); Organotitanium halogen ture ture Time fraction ether soluble Example number (rmnol) compound Mmol compound Mmol 0.) 0.) (hr.) (g.) fraction (g.)

2.0 O[Ti(OAo)a]2 0.2 AlC1 -0Et 0.6 78 30 16 0.24 0.25 2. 0 O[Ti(OA a}: 0. 2 AlEtClz O. 5' 78 -30 16 0. 15 0. l0 2. 0 O[Ti(OAc)a z 0. 2 SnClr 0. 5 78 -30 16 0. 01 0.08 2. 0 O[Ti(O 0):]2 O. 2 I; 0. 5 78 -30 16 0.07 0.32 2. 0 0 Tl(0A0)3]z 0. 2 78 30 16 0 0 2. 0 T1(O1-Pr)2(OAo)-2 0. 2 VOC1 0. 5 78 -30 16 1. 46 0. 74 2.0 Ti(Oi-Pr)2(OAo)z 0.2 In 0.5 78 -30 16 0.11 0.06 2. 0 Ti(Oi-Pr)2(OAc)2 0 2 78 -30 16 0 0 TABLE 3 Cata1ysts* Organotitanium compound,

Alternating copolymer of butadiene and propylene Catalyst Polymerization ll preparaconditions Intrinsic Microstructure of butadiene unit Organo- TiCl O C CuHs tion temviscosity aluminum perature Tem era- Time Yield [1,] Ois Trans 1,2 Example number compound Mmol (rmnol) C.) ture 0.) (hr.) (g.) (dl./g.) (percent) (percent) (percent) 0. 25 0. 10 -30 16 1. 92 3. 47 11 86 3 0. 25 0. 10 -20 -40 16 1. 89 4. 31 12 85 3 0.25 0. 10 -10 40 16 1. 78 4 59 13 84 3 0.25 0.10 0 40 16 1. 1t 4 81 22 75 3 0. 0. 025 78 -30 16 0. 13 0. 50 0. -78 -30 16 V O. 34 0. 50 0. 10 78 -30 16 0. 77 0. 0. 18 78 -30 l6 1. 41 0. 50 0. 20 78 -30 16 1. 46 0. 50 0. 23 78 30 16 1. 47 0. 50 0. 25 78 -30 16 1. 02 0. 50 0. 275 -78 -30 16 0. 64 0. 30 0.10 -30 -37 17 5 1. 81 3. 24 12 86 2 0. 30 0 10 78 20 25 1. 21 0. 62 0.50 0 20 -78 -30 16 0. 80

"Al(i-Bu) =triisobuty1aluminum, .AlEt ;=tr'iethylalurninum. Measured in chloroform at 30 C.

9 EXAMPLE 4 varying amounts of triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2.0 milliliters liquid propylene, 2.0 milliliters liquid butadiene and 2.0 milliliters toluene were put successively into the 5 bottles also employing the usual, dry, air-free technique.

Then, the bottles were sealed and allowed to copolymerize TABLE 4 Catalysts Organotitanium compound,

Polymerization Alternating copolymer of butadiene and propylene Catalyst conditions I [I prepara- Intrinsic Microstructure of butadiene unit Organo- T1Cl30 C OsH tion tem- Temperviscosity aluminum perature ature Time Yield [1,] Cis Trans 1,2 Example number compound Mmol (mmol) 0.) 0.) (hr.) (g.) (dl./g.)* (percent) (percent) (percent) 1 Al(i-Bu) 1. 00 0. 23 78 30 16 2. 62 1. 0O 0. 05 78 30 16 0. 0. 50 0. 05 78 30 16 0. 79 0. 25 0. O5 78 30 16 1. 25 0. 0. 05 78 30 16 0. 36 0. 30 0. 10 30 37 15 1. 57 0. 25 0.06 60 30 16 1 46 0. 25 O. 06 40 30 16 1 17 0. 25 0. 06 20 30 16 1. 17 0. 0. 06 0 16 0. 98 0. 25 0. 06 78 20 16 1. 57 0. 25 0. 06 78 10 16 1. 56 0. 50 0. 20 78 30 16 0. 33

Measured in chloroform at 30 C.

liquid butadiene and 2.0 milliliters toluene was put into the bottles also employing the usual, dry, air-free technique. Then, the bottles were sealed and allowed to copolymerize at predetermined temperature for 16 hours. The results were summarized in Table 4.

EXAMPLE 5 The usual, dry, air-free technique was employed and 8.0 milliliters toluene and varying amounts of organotitanium compound were put successively into 25 milliat predetermined temperature and for predetermined time. The results were summarized in Table 5.

EXAMPLE 6 The usual, dry, air-free technique was employed and 7.0 milliliters toluene, varying amounts of organotitanium compound and varying amounts of halogen compound were put successively into 25 milliliter glass bottles at 20 C. Then, the bottles were held in a low temperature bath at 78 C. (it corresponds to catalyst preparation temperature given in Table 6) and varying amounts of organoalurninum compound solution in tolune (1 molar solution) and a mixture of 2.0 milliliters liquid propylene, 2.0 milliliters liquid butadiene and 2.0 milliliters toluene were put successively into the bottles also employing the usual, dry, air-free technique. Then, the bottles were TABLE 5 Catalyst Polymerization Alternating copolymer of butadiene and propylene preparaconditions Catalyst tion Intrinsic Microstructure of butadiene unit tempera- Temperaviscosity i if l g ir lz o il n d Mmol EE"? g (dl./g.) (percegg 521i? (percerit? TlCMOCEt),

0.7 Same as above-...:; 0.1 78 30 17 0.26

O [TICKO (5150512 4..-; 0. 7 Same as above 0. 05 78 30 17 0.09

TICMOJJEt):

"Measured in chloroform at 3 liter glass bottles at 20 C. Then, the bottles were held in a low temperature bath at 78 C. (it corresponds to sealed and allowed to copolymerize at predetermined temperature and for predetermined time. The results were catalyst preparation temperature given in Table 5) and 75 summarized in Table 6.

13 EXAMPLE 8 The usual, dry, air-free technique was employed and 8.0 milliliters toluene and varying amounts of organotitanium compound were put successively into 25 milli- 14 the bottle was held ina low temperature bath at -78 C. and 0.60 milliliter triisobutylaluminum solution in toluene (1 molar solution), 1.0 milliliter liquid butadiene and 5.0 milliliters liquid propylene were put successively into the bottle also employing the usual, dry, air-free tech- !itef glass bottles at h Q were held 5 nique. Thereafter, the bottle was sealed and allowed to In 310W tempefafllfe bath at corresponds to copolymerize at 40 C. for 1.5 hours. The yield of the catalyst preparation temperature shown in Table 8) and alternating copolymer was 0 0 1.00 milliliter triisobutylaluminum solution in toluene (1 molar solution) was put into the bottles respectively. Thereafter, the bottles were held in a low temperature 10 EXAMPLE 11 bath at -78 C. and varying amounts of liquid propylene and varying amounts of liquid butadiene were put sucfi alr'free 9 1 was employed and cessively into the bottles also employing the usual, dry, mflhhtirs toluene mllhmole air-free technique. Then, the bottles Were sealed and 0 allowed to copolymerize at predetermined temperature 15 15 for 16 hours. The results were summarized Table 8. Tloho TABLE 8 Catalyst Organotitanium Alternating copolymer of butadiene and propylene compound,

Catalyst Monomers Polymerization O preparacondition Microstructure of butadiene tion Liquid Liquid unit; TiC13OCCflH5 temperapropylhuta- Tempera- Intrinsic H Example Al(i-Bu)' ture ene diene ture Time Yield viscosity is Trans 1.2 number (mmol) (mmol) 0.) (m1.) (ml.) 0.) (hr.) (g.) [1;](dI./g.)* (percent) (percent) (percent) *Measured in chloroform at 30 C.

EXAMPLE 9 a 4 7 2.0 milliliters-liquid butadiene, 2.0 milliliters liquid propylene and 0.5 milliliter triisobutylaluminum solution in The usual, dry, air-free techmque was employed and toluene (1 molar solution) were put successively into a 0.06 millimole 25 milliliter glass bottle at 30 C. Then, the bottle was sealed and allowed to copolymerize at -40 C. for 15.5 hours. The yield of the alternating copolymer was 1.63. TiClaOCHa The microstructure of butadiene unit of the copolymer was as follows: cis, 2%; trans, 95%; 1,2, 3%. was put into a 25 milliliter glass bottle at 20 C. Then, the bottle was held in a low temperature bath at -78 EXAMPLE 12 p C. and 0.25 milliliter triisobutylaluminum solution in toluone (1 molar solution), 10.0 milliliters liquid propylene 7 g fifi i was employed and and 2.0 milliliters liquid butadiene were put successively 6 He m1 m0 e into the bottle also employing the usual, dry, air-free technique. Thereafter, the bottle was sealed and allowed to copolymerize at 30" C. for 16 hours. The yield of the alternating copolymer of butadiene and propylene was I: 1 0.73 g. Intrinsic viscosity of the copolymer was 0.92 0 Ti DECK; a 2, (dl./g.).

EXAMPLE 10 The usual, dry, air-free technique was employed and I u 3 0 milliliters toluene d ()6 illi l 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and 0.5 millimole AlCl -O(C H were put successively into a 25 milliliter glass bottle at 40" C. Then, the bottle was held in a low temperature bath TlollqocoflHi at -78 C. and a mixture of 2.0 milliliters liquid propylene, 2.0 milliliters liquid butadiene and 2.0 milliliters toluwere put into a 25 milliliter glass bottle at 20 C. Then, one was put into the bottle also employing the usual, dry,

EXAMPLE 13 The usual, dry, air-free technique was employed and 10.0 milliliters toluene, 0.05 milliliter tert-butylchloride solution in toluene (1 molar solution) and 0.4 milliliter triisobutylaluminum solution in toluene (1 molar solution) were put into a 25 milliliter glass bottle at 25 C. Then the bottle was held in a low temperature bath at 32 C. and 0.12 millimole O l TlChO CH was put into the bottle. Thereafter, the bottle was held action was carried out. The yield of the alternating copolymer was 1.18 g. and its intrinsic viscosity was 2.65 (dl./ g.) in toluene at 30 C. From the experiments, the effect obtained by the addition of halogen compound can be found.

EXAMPLE 14 The usual, dry, air-free technique was employed and 7.0 milliliters toluene and varying amounts of organotitanium compound were put into milliliter glass bottles at 20 C. Then, the bottles were held in a constant temperature bath showing predetermined temperature (it corresponds to catalyst preparation temperature given in Table 9) and varying amounts of organoaluminum compound solution in toluene (1 molar solution) was put into the bottles respectively. Thereafter, the bottles were held in a low temperature bath at -78 C. and varying amounts of liquid a-olefin and 2.0 milliliters liquid butadiene were put successively into the bottles also employing the usual, dry, air-free technique. Then, the bottles were sealed and allowed to copolymerize at predetermined temperature and for predetermined time. The results were summarized in Table 9.

TABLE 9 Alternating copolymer of P 1 I ti butadiene and o ymer za on e0 0 ero Catalysts Catalyst Monomers condition i-oiiin prepara- Organo- Organotion tem- Liquid Intrinsic Example aluminum titanium perature Liquid buta- Tempera- Time Yield viscosity number compound Mmol compound Mrnol 0.) a-OlBfiIl Ml. diene NJ. ture 0.) (hr.) (g.) [1 (dl./g.) 1 Al(i-Bn)a 11 0.5 0.1 ---78 Styrene"--- 3.0 BD 2.0 a0 21 0.14

TlClsO CHa I 2 Aid-Bu); 0.5 Same as above-. 0.1 78 Butane-1.... 2.0 BD 2.0 16 1.38 1.28

3 Al(i-Bu)a 0.6 (H) 0.06 4MP1- 2.0 BD 2.0 40 21 0.18

TiCIaOCCaHa 4 Al(hexyl)a 0.5 H 0.2 0 HeXene-L.-- 6.0 BD 1.0 40 )6 0.61 0.8

TiGlz(OGEt)l "4-MP-1=4-methyl-penten-1, BD =butadiene. "Measured in chloroform at 30 C.

in a low temperature bath at -78 C. and a mixture of EXAMPLE 15 2.0 milliliters liquid propylene, 2.0 milliliters liquid butadiene and 2.0 milliliters toluene was put into the bottle also employing the usual, dry, air-free technique. Then,

the bottle was sealed and allowed to copolymerize at -40 C. for 16 hours. The yield of the alternating copolymer of butadiene and propylene was 1.37 g. and its intrinsic viscosity was 2.8 (dl./ g.) in toluene at 30 C. By using the two components catalyst-system of 0.4 millimole triisobutylaluminum and 0.12 millimole 0 TiChOJ JCHa,

butadiene and propylene alternating copolymerization re- 'low temperature bath at 78" C. and vary amounts of liquid u-olefin and 2.0 milliliters liquid butadiene were put successively into the bottles also employing the usual, dry, air-free technique. Then, the bottles were sealed and allowed to copolymerize at predetermined temperature and for predetermined time. The results were summarized in Table 10.

milliliter triethylaluminum solution in toluene (1 molar solution) was put into the bottle. Thereafter, the bottle was held in a low temperature bath at 78 C. and 4.0 milliliters liquid pentene-l and 2.0 milliliters liquid butadiene were put successively into the bottle also employing the usual, dry, air-free technique. Then, the bottle was sealed and allowed to copolymerize at 20 C. for 48 hours. MEK soluble alternating copolymer of butadiene and pentene-l was obtained. Its yield was 0.40 g.

What is claimed is:

1. A process for preparing 1:1 copolymer of butadiene and an tit-olefin having alternating butadiene and a-olefin units, said a-olefin having the general formula of CH =CHR wherein R represents a G hydrocarbon radical selected from the group consisting of alkyl, cycloalkyl, aryl and aralkyl radicals which comprises contacting said butadiene and said u-olefin in liquid phase with a catalyst composed of (A) an organoaluminum compound having the general formula of AlR wherein R is as defined above and (B) an organotitanium compound having XTiO R (R is as defined above and X is halogen) structure in the molecule.

2. A process as claimed in claim 1 wherein a halogen, a halogen compound selected from the group consisting of a halide or oxyhalide having Lewis acid property, a Lewis base complex compound of said halide or oxyhalide, an organoaluminum compound having Al-X linkage (X is halogen), an organotransition metal compound having transition metal-X linkage (X is halogen), an acid halide, a compound having the general formula of (X is halogen) and a halogenated alkane or a mixture thereof, is further included as a component of the catalyst.

3. A process as claimed in claim 1 wherein the atomic ratio of aluminum atom contained in the organoaluminum compound to titanium atom contained in the organotitanium compound is within a range from 1 to 200'.

4. A process as claimed in claim 2 wherein the atomic ratio of titanium atom contained in the organotitanium compound to the halogen or halogen atom contained in the halogen compound is within a range from 0.01 to 20.

5. A process as claimed in claim 1 wherein the molar ratio of butadiene to said wolefin in the initial monomer composition is within a range from 10:1 to 1:100.

6. A process as claimed in claim 1 wherein said organoaluminum compound and said organotitanium compound are mixed at a temperature within a range from -100 C. to +100 C.

7. A process as claimed in claim 2 wherein said halogen, halogen compound or a mixture thereof is mixed with the other catalyst components at a temperature within a range from -l00 C. to +100 C.

8. A process as claimed in claim 1 wherein polymerization reaction is carried out at a temperature within a range from C. to 100 C.

9. A process as claimed in claim 8 wherein said temperature is within a range from 78 C. to +50 C.

10. A process as claimed in claim 3 wherein the molar ratio of butadiene to said (IL-Olefin in the initial monomer composition is within a range from 5:1 to 1:50, the atomic ratio of aluminum atom contained in the organo aluminum compound to titanium atom contained in the organotitanium compound is within a range from 2 to 100, said organoaluminum compound and said organotitanium compound are mixed at a temperature within a range from 78 C.- to +50 C., and polymerization temperature is within a range from 78 C. to +50 C.

11. A process as claimed in claim 10 wherein the R used in the general formula to identify said a-olefin represents C -C hydrocarbon radical, and the R used in the general formula to identify said organoaluminum com pound represents C -C hydrocarbon radical.

12. A process as claimed in claim 4 wherein the molar ratio of butadiene to said a-olefin in the initial monomer composition is within a range from 5:1 to 1:50, the atomic ratio of aluminum atom contained in the organoaluminum compound to titanium contained in the organotitanium compound is within a range from 2 to 100, the atomic ratio of titanium atom contained in the organotitanium compound to the halogen or halogen atom contained in the halogen compound is within a range from 0.02 to 10, the catalyst components are mixed at a temperature within a range from 78 C. to +50 C. and polymerization reaction is carried out at a temperature within a range from 78 C. to +50 C.

13. A process as claimed in claim 12 wherein the R used in the general formula to identify said a-olefin represents a C -C hydrocarbon radical, and the R used in the general formula to identify said organoaluminum compound represents a C -C hydrocarbon radical.

References Cited UNITED STATES PATENTS 3,590,024 6/1971 Ishizuka et al. 260-853 R 3,652,518 3/1972 Kawasaki et a1. 26085.3 R 3,652,519 3/ 1972 Kawasaki et a1. 26085.3 R 3,217,496 5/1967 Natta et al. 260-882 3,470,144 9/1969 Minekawa et al. 260-853 FOREIGN PATENTS 1,010,790 11/1965 Great Britain 260-853 1,026,615 4/ 1966 Great Britain 26085.3 1,108,630 4/1968 Great Britain 260-853 546,150 9/1956 Belgium 26085.3

0 JOSEPH L. SCHOFER, Primary Examiner A. HOLLER, Assistant Examiner US. Cl. X.R. 26084.1, 85.3 R

UNITED STATES PATENT OFFICE CERTEHCATE OF CORRECTICN Patent No. 3 737,416 Dated June 5, 1973 lnventofls) AKIHIRO KAWASAKI et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 4 Delete "Kiyoshige Hayashi" from identification of inventors;

lines 9-10 Delete "July 24,1970. .45/97,l33"

from identification of priority claims;

line 15 After "ct-olefin" insert -and.

Column 2, line 2 Delete "blocked" and replace with -block-;

line 48 Before "vanadium-halogen" insert ---vanadium compound having-;

line 49 Delete "hydrogen" and replace with hydrocarbon;

line 65 Before "Ger." insert Column 5, line 44 Delete "methylheptene" and replace with --methyl-heptene;

Signed and Scaled this ninth Day Of September 1975 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer (vmmissinncr njlarenls and Trademarks UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTEGN Patent No. 6 Dated June 5, 1973 cars in the aboveidentified patent It is certified that erro A :eby corrected as shown below:

and that said Letters Patent are n Column 5, line 48 Delete "conjugated diene" and replace with butadiene;

line 72 Rewrite "peferred" as -preferred--.

Column 6, line 24 Rewrite "prduct" as product.

Column 7, Table 1 In footnote "B%.OET should be deleted and rewritten as BF -OEt Column 8, Table 2, last column In heading de'lete d ethyl" and rewrite as -diethyl.

Column 9, Table 5 third column Re Examples 1, 3 and 5,

- C in place of C In first footnote, second compound should be written as O ll T1Cl (OCC H Signed and Scaled this ninth Day Of September 1975 [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Altesling Officer Commissioner ojPuIenIs and Trademarks Patent No. 16 Dated June 5 1973 inventofls) AKIHIRO KAWASAKI et al Page 5 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 10, line 44 Delete "tolune" and rewrite as --toluene- Column ll, Table 6, fourth column Re Examples 2, 3 and 4,

delete "Same as above. .do (second occurrence) and replace with Q I! TiCl (OCEt) 3 TiCl (OCEt) Same as above-;

last column, re Example 1, insert --7---.

Columns 15 and 16, Table 9 fourth column Re Example 1,

compound should be written as ll -TiCl OCCH last column, in main heading, after En'gncd and Sealed this ninth Day of September 1975 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner uflarenrs and Trademarks UNITED STATES PATENT oTT'IcE CERTIFXCATE 0F CORRECTEON Patent No. 3,737,416 Dated June 5, 1973 AKIHIRO KAWASAKI et al Inventor(s) Page Q It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 16, line 69 Rewrite "vary" as -varying.

Column 18, Example 16, line 8 Rewrite "mililiters" as milliliters.

Columns 7, 9, ll, l2, l3, l5, l7, l8 and 19 Tables l-l2 In all Tables, column 1 thereof, delete "Example number" and replace with -Experiment number-.

Signed and Sealed this A nest:

RUTH C. MASON Alresling Officer C. MARSHALL DANN (ummisxiuner of Parents and Trademarks 

